US2652397A - Sensitizing dyes containing a 2-acylamino-5(4)-thiazolone nucleus - Google Patents

Sensitizing dyes containing a 2-acylamino-5(4)-thiazolone nucleus Download PDF

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US2652397A
US2652397A US203525A US20352550A US2652397A US 2652397 A US2652397 A US 2652397A US 203525 A US203525 A US 203525A US 20352550 A US20352550 A US 20352550A US 2652397 A US2652397 A US 2652397A
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dye
thiazolone
those
gelatino
acylamino
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Aubert Per
Edward B Knott
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to BE508127D priority Critical patent/BE508127A/xx
Priority to BE508128D priority patent/BE508128A/xx
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Priority to US203526A priority patent/US2656353A/en
Priority to US203525A priority patent/US2652397A/en
Priority to GB30098/51A priority patent/GB689025A/en
Priority to FR1105161D priority patent/FR1105161A/fr
Priority to FR1105160D priority patent/FR1105160A/fr
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups

Definitions

  • This invention relates to merocyanine dyes containing a z-acylamino-fim) -thiazolone nucleus and to a method Ior preparing them.
  • the new merocyanine dyes of can be represented mula:
  • R represents an alkyl group, such as methyl, ethyl, nepropyl, isopropyl, nt-butyl, isobutyl, n-amyl, n-octyl, fiehydroxyethyl, ,B-ohloroethyl, fi-acetoxyethyl, etc. groups (especially alkyl groups of the formula C I-Iz c wherein m represents a positive integer of from 1 to 8), R represents the acyl group. of a. carboxylic acid, e.
  • L represents a mefih ne r up (subs i ut d and u su sti u ed, e. g., ;,CH.., CR'mwhere B. represents an alkyl group, such as methyl, ethyl, etc.), n rep-.- resents a positive integer from 1 to 2, d represents a.
  • benzothiazole 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-ch lorobenzothiazole, 7-ch1orobenzothiazole, siemethylbenzothiazole, 5:1'I1Qthy1b6IlZQt1'll8Z01B, B-methylbenzothiezole, 5-bromobenzothiazole, 6-.-bromo ben zothiazole, ephenylbenzothiazole, 5ephenylbenzqthiezole, 4-methoxyhenzothiazole, 5emeth xybenzothiazole, G-methoxybenzothiazole, 5- ioclobenzothiazolfl.
  • a-naphthothiazole fi-naphthothiazole, 5-methoxy-p-naphthothiazole, 5 ethoxy 8 naphthothiazole, 8- methoxy-a-naphthothiazole, 7-methoxy-a-naphthothiazole, etc.
  • those of the thionaphtheno 'i, 6', 4,5-thiazole series e. g. 4'-methoxythionaphtheno-7, 6, 4,5-thiazole, etc.
  • those of the oxazole series e. g.
  • benzoxazole fi-chlorobenzoxez'ole, 5-methy1benzoxazole, 5-phenylbenzoxazo1e, fi met'hylbenzoxazole, 5,6-dimethylhenzoxazole, 4,6-dimethylbenzoxazole, 5-methoxybenzoxazole, 5-ethoxybenzoxazole, 5-chlorobenzoxazole, S-methOXybenzoxazole, 5-hydroxybenzoxazole, 6 hydroxybenzoxazole, etc.), those of the naphthoxazole sea-naphthoxazole, e-naphthoxazole,
  • those of the selenazole series e. g. 4- methylselenazole, 4-phenylselenazo1e, etc.
  • those of the benzoselenazole series e. g. benzoselenazole, fi-chlorobenzoselenazole, S-methoxyben'zoselenazole, 5.-hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.
  • those of the nephthoselenazole series e. g. a-naphthoselenazole, 5- naphthoselenazole, etc.
  • those of the thiazoline series e. g.
  • thiazoline, 4-methylthiazoline, etc. those of the 2-quinoline series (e. g. quinoline, 3-methylquinoline, fi-methylquinoline, 7-methylquinoline, 8-methylquinoline, fi-chloroquinoline, 8echloroquinoline, fi-methoxyquinoline 6- ethoxyquinoline, fi-hydroxyquinoline, B-hydroxyquinoline, etc.), those of the 4i-quinoline series (e. g. quinoline, 6-methoxyquinoline, '7-methylquinoline, 8-.methylquino1ine, etc.), those of the l-isoquinoline series (e. g.
  • Ra represents a hydrogen atom, an alkyl group (9. g. methyl, ethyl, etc.) or the any] group Hz 43-NHR1 EX III.
  • R1 has the values set forth above and X represents an acid radical, e. g. chloride, bromide, acetate, etc.
  • X represents an acid radical, e. g. chloride, bromide, acetate, etc.
  • the condensations are advantageously carried out in the presence of an acidbinding agent, e. g. the trialkylamines, such as triethylamine, tri-n-butylamine, etc., dialkylanilines, such as N,N-dimethyl-, N,N-diethylamlines, etc, heterocyclic tertiary amines, such as pyridine, quinoline, N-alkylpiperidines, etc., alkali metal alcoholates, such as sodium ethylate, etc.
  • an acidbinding agent e. g. the trialkylamines, such as triethylamine, tri-n-butylamine, etc., dialkylanilines, such as N,N-di
  • the condensations can also be carried out in the presence of an inert diluent, such as methanol, ethanol, n-pr-opanol, isopropanol, n-butanol, diethyl ether, acetone, lA-dioxane.
  • an inert diluent such as methanol, ethanol, n-pr-opanol, isopropanol, n-butanol, diethyl ether, acetone, lA-dioxane.
  • the merocyanine dyes of Formula I above where d is 1 can be prepared by condensing a cyclammonium quaternary salt selected from those represented by the following general formula:
  • R, Z, X1, and n have the values set forth above
  • R4 represents an alkyl group, such as methyl, ethyl, etc., or an aryl group, such as phenyl o-, m-, and p-tolyl, etc., with a 2-acy1- amino-5 (4) -thiazo1one acid-addition salt selected from those represented by Formula III above.
  • the condensations can advantageously be carried out in the presence of an acid-binding agent, such as the trialkylamines (e. g. triethylamine, tri-n-butylamine, etc.) dialkylanilines (e. g.
  • the condensations can also be carried out in the presence of an inert diluent, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, diethyl ether, acetone, lA-dioxane, etc.
  • Example 1 [2-(1-ethyZqmnoline)l [at-acetamin0-5 (4) -thiazolonel dimethinemcrocyanine solution was refluxed for 5 minutes, and the reaction mixture was chilled. The precipitate was collected on a filter and then dissolved in warm benzene. The benzene solution was cooled whereupon the desired dye was obtained as green crystals having a melting point of 233 C. It sensitized a gelatino-silver chloride emulsion to 660 m with a maximum lying between 500 and 600 mu.
  • Example 2. [4-(1-ethylqu'inoline)l [4-(2-acetamino-5 (4) -thiazolonel dimethinemerocyanine
  • This dye was prepared in the same manner as the dye of Example 1 by replacing the 2-[3-acetanilidovinylquinoline ethiodide by a molecularly equivalent amount of 4-eacetanilidovinylquinoline ethiodide, and by recrystallizing the product dye from ethanol instead of benzene. It was obtained as a dark green powder melting at 226 0.
  • Example s.-[2- (s-emyzbenzomzozen [4- 2- acetamz'no-5 (4) -thz'aeolone) dimethznemerocyam'ne 1.2 g. of 2-acetamino-5(4)-thiazolone hydro bromide and 2.2 g. of 2-pacetanilidovinylbenzoxazole ethiodide were dissolved in a mixture of 5 cc. of ethanol and 1.4 cc. of triethylamine. The solution was refluxed for 5 minutes, and then chilled. The precipitate was collected on a filter and then dissolved in warm chloroform.
  • the chloroform solution was cooled, whereupon the desired dye separated in the form of red needles with a bluish lustre having a melting point of 264 ,0. (turned orange about (3.). It sensitized a gelatino-silver chloride emulsion strongly to 600 m with maxima at 450 and 520 m It sensitized a gelatino-silver bromiodide emulsion to 560 m with a maximum at 530 m Example 4.
  • Emmfle ylbenzothiazolell [4-(2- acetamino 5-(4) -thiaaolone] dtmethinemerocyanine 1.2 g. of Z-acetaminQ-SIG) thiaz'olone hydrobromide and 2.35 g. of'z fl acetanilidovinylbenzothiazole ethiodide were-dissolved in a mixture of 5 pool ethanol and 1,4 cc. of 'triethylamine.
  • Example 7 [2- (3-eth1 Ihenzaelenazole) LM-(Z- acetamino (4) -thiaz0l0ne) ⁇ ]wdimethinmer0- cyam'ne Se oigcs ⁇ O s en-(m d Emmion.
  • Example 9 The prebipitate was collected on a filter and th'emdissolveddn warm Example 9.--[2-(3-,ethylbenzomazole,)l [4-(2-11- butyramino 5(4) -thiazolonel tetramethinemerocyanine benzoxazole ethiodide,:1):7:.g.sotzfi nebutyramino- "5 4) -thiazolone hydrobromide, cc.. of ethanol, and 0.8 cc. of -triethylamine were 1 refluxed atogether 'for 3 minutes. The reactiommixture was then :cooled and t the precipitate collected .on a filter.
  • the dye was obtained as orange prisms having a melting point of 229 C. It sensitized a gelatino-silver chloride emulsion with a maximum at 500 m
  • the 2-acylamino-5(4) -thiazolone acid addition salts used in the above examples were obtained as follows:
  • Example 14.2-acetamino-5(4)-thiazolone hydrobromide 8.8 g. of acetylthiohydantoic acid (Wheeler et al.-Amer. Chem. Jour., vol. 46 (1911), Pg. 469) were dissolved in 45 cc. of anhydrous dioxane and 30 cc. of diethyl ether, and 10 cc. of phosphorous tribromide were added. The solution was shaken gently and then stirred manually for several minutes until the whole solidified. The solid was shaken with diethyl ether, and the ether then decanted off. There was obtained a 95 percent yield of the desired intermediate having a melting point of 159 C. It fumed strongly in moist air, but remained stable when stored in a desiccator.
  • our new dyes spectrally sensitize photographic silver halide emulsions when incorporated therein.
  • the dyes are especially useful for extending the spectral sensitivity of the customarily employed gelatino-silverchloride, gelatino-silver-chlorobromide, gelatinosilver-bromide and gelatino-silver-bromiodide developing-out emulsions.
  • the extent to which gelatino-silver bromiodide developing-out emulsions can be sensito add the dyes to the emulsions in the form appropriate solvent. Methanol or acetone has proved satisfactory as a solvent for most of our new dyes.
  • the particular solvent used will, of course, depend-on-thesolubility properties of the particular dye.
  • the concentration of the'dyes in the emulsions be diluted with water, containing from to 100 mg. of dye, is slowly added to about 1000 cc. of gelatino-silver-halide emulsion, with stirring. Stirring is continued until the dye is thoroughly dispersed in the emulsion.
  • the dyes can be incorporated in photographic emulsions by any of the other methods customarily employed in the art, e. g. by bathing a plate or film upon which an emulsion is coated in a solution of the dye in an appropriate solvent. However, bathing methods are ordinarily not to be preferred.
  • Emulsions sensitized with the dyes can be coated on suitable supports, such as glass, cellulose derivative film. resin film or paper in the usual manner.
  • a merocyanine dye selected from those represented by the following general formula:
  • R represents an alkyl group containing from 1 to 8 carbon atoms
  • R1 represents the acyl group of a carboxylic acid
  • L represents a methine group
  • n represents a positive integer from 1 to 2
  • d represents a positive integer from 1 to 3
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of 10 1 the thia'zole series, those of the ben'zothiazole series, those of the naphthothiazole series, those of the thiOIiaphtheIlD-Tfi,4,5' thiaZo1e series, those of the oxazole those of the benzoX- the 3 isoquinolin e series, those of the 3,3-di- V 2.
  • the merocyani ne' dye represented by the following formula:
  • the merocyanine dye represented by the '7 A method for making merocyanine dyes comprising condensing an acid-addition salt of a 2-acylamino-5(4)-thiazolone selected from tholse represented by the following general formu a:
  • R1 represents an acyl group of a carboxylic acid
  • X represents an acid radical with a cyclammonium quaternary salt selected from those represented by the following general formula:
  • R represents an alkyl group
  • X1 represents an acid radical
  • n represents a positive integer of from 1 to 2
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring
  • D represents a member selected from the group consisting of an alkylmercapto group, an arylmercapto group, a ,8- arylaminovinyl group, and a 6-arylamino-l,3- butadienyl group.
  • a method according to claim '7 for making merocyanine dyes comprising condensing an acidaddition salt of a 2-acylamino-5(4) -thiazo1one with a 2-,B-acetanilidovinylquinoline alkyl salt wherein the alkyl group is an alkyl group of the formula CmH2m+1 wherein m represents a positive integer of from 1 to 8.
  • a method according to claim '7 for making merocyanine dyes comprising condensing an acidaddition salt of a 2-acylamino-5(4)-thiazolone with a 2-(3-acetanilidovinylbenzothiazole alkyl salt wherein the alkyl group is an alkyl group of the formula cmH2m+l wherein m represents a positive integer of from 1 to 8.
  • a method according to claim '7 for making merocyanine dyes comprising condensing an acid-addition salt of a 2-acylamino-5( l)thiazolone with a 2-[3-acetanilidovinylthiazoline alkyl salt wherein the alkyl group is an alkyl group of the formula CmH2m+1 wherein m represents a positive integer of from 1 to 8.
  • a method according to claim '7 for making merocyanine dyes comprising condensing an acid-addition salt of a 2-acylamino-5(4)-thiazolone with a 243-acetanilidovinylbenzoxazole alkyl salt wherein the alkyl group is an alkyl group of the formula CmH2m+1 wherein m is a positive integer of from 1 to 8.
  • a method according to claim '7 for making merocyanine dyes comprising condensing an acidaddition salt of a 2-acylamino-5(4)-thiazolone with a Z-B-acetanilidovinylbenzoselenazole alkyl salt wherein the alkyl group is an alkyl group of the formula CMHZm-i-l wherein m represents a positive integer of from 1 to 8.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
US203525A 1950-12-29 1950-12-29 Sensitizing dyes containing a 2-acylamino-5(4)-thiazolone nucleus Expired - Lifetime US2652397A (en)

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Application Number Priority Date Filing Date Title
BE508127D BE508127A (en, 2012) 1950-12-29
BE508128D BE508128A (en, 2012) 1950-12-29
US203526A US2656353A (en) 1950-12-29 1950-12-29 Sensitizing dyes containing a 2-thio-2, 5 (3, 4)-thiazoledione nucleus
US203525A US2652397A (en) 1950-12-29 1950-12-29 Sensitizing dyes containing a 2-acylamino-5(4)-thiazolone nucleus
GB30098/51A GB689025A (en) 1950-12-29 1951-12-24 Merocyanine dyes and methods of making them and photographic silver halide emulsions containing them
FR1105161D FR1105161A (fr) 1950-12-29 1951-12-28 Nouveaux colorants de la série des mérocyanines et leurs applications notamment en photographie
FR1105160D FR1105160A (fr) 1950-12-29 1951-12-28 Nouvelles mérocyanines et leurs applications, notamment en photographie

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BE (2) BE508128A (en, 2012)
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2078233A (en) * 1934-09-14 1937-04-27 Eastman Kodak Co Photographic emulsion
US2170804A (en) * 1937-04-24 1939-08-29 Eastman Kodak Co Merocyanine dyes from benzoxazoles
US2177402A (en) * 1935-11-15 1939-10-24 Eastman Kodak Co Dye from thiazolones

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2078233A (en) * 1934-09-14 1937-04-27 Eastman Kodak Co Photographic emulsion
US2177402A (en) * 1935-11-15 1939-10-24 Eastman Kodak Co Dye from thiazolones
US2170804A (en) * 1937-04-24 1939-08-29 Eastman Kodak Co Merocyanine dyes from benzoxazoles

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FR1105161A (fr) 1955-11-28
BE508128A (en, 2012)
GB689025A (en) 1953-03-18
BE508127A (en, 2012)
FR1105160A (fr) 1955-11-28

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